Dental coating materials

ABSTRACT

Polymerizable materials which contain (1) 1 to 80 wt.-% of at least one polysiloxane, (2) 0.1 to 5 wt.-% of one or more initiators for radical polymerization, (3) 0 to 60 wt.-% of radically polymerizable monomer and (4) 1 to 50 wt.-% of one or more radically polymerizable monomers which carry at least phosphonic acid group, sulphonic acid group and/or mono- or dihydrogen phosphoric acid ester group, the polysiloxane (1), the monomer (3) or both being substituted by fluorine. The materials are suitable in particular for the coating of natural or artificial teeth.

The present invention relates to coating materials which are suitable inparticular for dental purposes and can, for example, prevent theformation of plaque and the development of caries on dental substrates,in particular on natural teeth.

It is known to coat the tooth structure, above all of the tooth enameland the dentine, for protection during dental treatment, as mechanicalprotection against ageing processes, for cosmetic reasons, to treathypersensitivities or to prevent caries, gingivitis and periodontitis.For these purposes various materials are described in the state of theart.

EP 0 089 187 discloses protective varnishes which, along with vinylacetate/vinyl chloride copolymer, contain a further copolymer which,along with vinyl acetate and vinyl chloride units, has carboxylic acidor carboxylic acid anhydride groups. The copolymers are dissolved inorganic solvent.

DE 37 17 762 discloses a coating material based on polystyreneresin/rosin or rosin derivatives, dissolved in an organic solvent. Thematerials are provided to protect tooth surfaces against anunintentional etching.

Varnishes based on carbamide peroxide, film-formers and solvents for thebrightening of teeth are known from U.S. Pat. No. 6,083,421.

WO 99/15131, EP 0 897 7099, EP 1 216 681, EP 1 138 308, EP 0 716 845 andWO 02/26196 disclose coating materials which, along with film-formingpolymer and organic solvent, contain pigments such as titanium dioxideand mainly serve to provide the tooth surface with a white coating.

U.S. Pat. No. 5,133,957 discloses adhesive protective films for thedesensitizing of hypersensitive teeth, based on monomer mixtures e.g.from the reaction product of N-phenylglycine or N-(p-tolyl)glycine withglycidyl methacrylate and monomers which are accessible by reactinganhydrides with hydroxyethylene methacrylate.

In U.S. Pat. No. 5,330,746, U.S. Pat. No. 5,403,577, U.S. Pat. No.5,139,768 and EP 0 381 445 therapeutics for application to the toothsurface are described which contain strontium or potassium salts in acarrier varnish and are intended to be suitable for treatinghypersensitivities in the area of the neck of the tooth.

In DE 36 34 697 a varnish for combating cariopathogenic germs such asStreptococcus mutans and lactobacilli is described which contains, asactive ingredients, chlorhexidine digluconate and thymol and/orcarvacrol.

U.S. Pat. No. 4,883,534 and EP 0 428 520 disclose varnish systems basedon chlorhexidine. Moreover varnishes with other antibacterial activeingredients such as triclosan (2,4,4′-trichloro-2′-hydroxydiphenylether) (WO 99/20227 and WO 98/48766), cetylpyridinium chloride orbenzalkonium chloride (EP 0 900 560) are known from the state of theart. These are mostly so formulated that the active ingredient isphysically dissolved, in an organic solvent together with a film-formingpolymer.

Fluoridation varnishes for the prevention of caries are described inU.S. Pat. No. 3,969,499, DE 24 17 940 and DE 100 40 716.

U.S. Pat. No. 4,324,630 and WO 00/09030 disclose protective varnisheswhich are also intended to prevent an acid attack on the tooth structurewithout fluoride.

Moreover coating materials based on hydrolytically condensable andradically polymerizable silanes are known. The hydrolytic condensationof these silanes leads to polysiloxanes which can be cured thermally,photochemically or by redoxinitiation via polymerizable organic groups(C. J. Brinker, G. W. Scherer, Sol-Gel-Science, Acad. Press, Boston etc.1990, 839ff.). Inorganic/organic networks are obtained (H. Schmidt, Mat.Res. Soc. Symp. Proc. Vol. 32 (1984) 327-335; H. Schmidt, H. Wolter, J.Non-Cryst. Solids 121 (1990) 428-435).

EP 0 450 624 B1 discloses polysiloxane-containing materials which areintended to be suitable in particular for the coating of metals,plastics, paper, ceramics, wood, glass and textiles. The polysiloxanesare prepared by reaction of silanes and optionally furtherhydrolytically condensable compounds, for example of B, Al, P, Sn andPb. The coating materials can moreover contain unsaturated organiccompounds and can be cured by light or thermally depending on the choiceof polymerization.

Similar polysiloxanes which are intended to be suitable as dentalcoating materials are known from DE 41 33 494 C2.

In DE 40 11 045 C2 and EP 0 107 0499 A1 varnishes for the coating ofplastic substrates are described which, along with a silane withethylenically unsaturated groups, contain a second silane with amercapto radical. The materials are also able to be cured by UV-lightwithout adding a photoinitiator.

DE 41 18 184 A1 discloses, coating compositions, based onfluorine-containing inorganic polycondensates which are intended to besuitable for the coating of glass, ceramic, metal, plastics and paperand are to be characterized by good anti-adhesion properties. DE 195 44763 A1 proposes the use of these materials for the coating of braces anddentures.

According to DE 195 35 729 A1 the coating of dentures and teeth with thecompositions of DE 41 18 184 A1 is intended to protect these against acolonization of their surface by microorganisms.

Coating materials are known from EP 0 171 493 B1 based on inorganicpolycondensates of soluble zirconium compounds and organofunctionalsilanes which is intended to allow a scratch-resistant coating ofplastic lenses and plastic spectacle glasses.

DE 38 36 815 A1 proposes an improvement of the materials known from EP 0171 493 by addition of organic compounds which have functional groupswhich are activated only during the course of or after the end ofcuring, such as blocked polyisocyanates and polyesters.

Sol-gel compositions are known from EP 0 595 840 B1 and EP 0 595 844 B1,starting from non-radically polymerizable alkoxides such as e.g.tetraethoxy silane, zirconium tetra-sec.-butoxide or aluminiumtri-sec.-butoxide, which, after hydrolytic condensation, are intended tobe suitable for the coating of natural teeth. Curing with laser beams orgas flame is to result in glass-like coatings.

WO 92/16183 discloses compositions based on organically modified silicicacid polycondensates which are intended to be suitable for the coatingof teeth and denture parts. The cured coatings are to be resistant toplaque accumulation.

WO 95/15740 and U.S. Pat. No. 6,312,668 relate to orally applicablecoating materials based on polysiloxane-modified organic polymers. Theseare obtained by subjecting silanes with polymerizable side groupstogether with further components to a radical polymerization. Thesilanes can contain hydrolytically condensable groups which are intendedto facilitate a condensation of the polymers following thepolymerization. The final-curing of the materials takes place,optionally after the addition of further monomers, by renewed radicalpolymerization via polymerizable radicals which have remained in thepolymer.

The chemical composition and the wetting behaviour of the known coatingmaterials and the natural tooth structure (enamel and dentine) clearlydiffer from each other. Organically modified polysiloxanes normally havehydrophobic properties, whereas the tooth structure has a hydrophiliccharacter. Although it is known that hydrophobic coating materials areadvantageous as regards the prevention of a colonization of the toothsurface by microorganisms, on the other hand they adversely effect auniform wetting of the tooth surface and the adhesion of the materials,so that a pre-treatment of the tooth surface with acids and optionallyadhesion promoters becomes necessary. The acid treatment can in turnnecessitate the protection, with suitable protective coatings, of teeththat are not to be treated, which additionally increases the overallcost of the treatment.

The object of the invention is to provide coating materials which aresuitable in particular for dental purposes and which show a good wettingbehaviour as well as a high self-adhesion, in particular to the surfaceof artificial and natural teeth, but which simultaneously effectivelysuppress the accumulation of microorganisms, in particular of plaque,and other undesired components.

According to the invention this object is achieved by polymerizablematerials which contain

-   (1) 1 to 80 wt.-%, preferably 20 to 60 wt.-% and particularly    preferably 30 to 50 wt.-% of at least one polycondensate based on    -   (A) one or more radically polymerizable silanes of Formula (I)        (R¹ _(a)—R²)_(m)R³ _(n)SiX_((4-m-n))  (I),    -    in which R¹ is a radically polymerizable group, R² is absent or        is a di- (a=1) or trivalent (a=2) substituted or unsubstituted        hydrocarbon radical with 1 to 30 hydrocarbon atoms, the carbon        chains of the hydrocarbon radical being able to be interrupted        by 1 or more, preferably 1 to 5, heteroatoms, in particular O        and/or S, 1 or more, preferably 1 to 5, carboxylic acid ester        groups (—CO—O— or —O—CO—), carboxylic acid amide groups        (—CO—NR⁷— or —NR⁷—CO— with R⁷=H or C₁-C₅ alkyl), urethane groups        (—HN—CO—O— or —O—CO—NH—) and/or amino groups (—NR⁸— with R⁸=H or        C₁-C₅ alkyl), R³ is C₁-C₁₂ alkyl or C₃-C₁₂ cycloalkyl, radical a        C₆-C₁₂ aryl radical, C₆-C₁₂ arylalkyl or C₆-C₁₂ alkylaryl, X is        halogen or a C₁-C₃ alkoxy radical, a is 1 or 2, m is an integer        from 1 to 3 and n is an integer from 0 to 2, the sum of m and n        being not greater than 3, and optionally    -   (B) one or more silanes according to Formula (II)        R⁴ _((4-p))SiY_(p)  (II),    -    in which R⁴ is a C₁-C₁₂ alkyl radical or phenyl radical, which        can be substituted in each case by —NH₂, —SH or —F, Y is halogen        or a C₁-C₃ alkoxy radical- and p is an integer from 1 to 4,        and/or    -   (C) one or more metal compounds of Formulae, (III) and/or (IV)        AlZ₃  (III)        Me(O)_(r)Z_(s)  (IV),    -    in which Z is halogen or a C₁-C₆ alkoxy radical, Me is        zirconium or titanium r is 0 or 1, s is an integer from 1 to, 4,        the sum of the valencies of the radicals O and Z corresponding        to the valency of the metal,-   (2) 0.1 to 5 wt.-%, preferably 0.2 to 3 wt.-% and particularly    preferably 0.5 to 2 wt.-% of one or more initiators for the radical    polymerization and-   (3) 0 to 60 wt.-%, preferably 20 to 55 wt.-% particularly preferably    30 to 50 wt.-% organic, radically polymerizable monomer.

The materials are characterized in that they contain in addition

-   (4) 1 to 50 wt.-%, preferably 5 to 30 wt.-%, particularly preferably    10 to 20 wt.-% of one or more radically polymerizable monomers of    Formula (V),    R⁵ _(t)-Sp-A_(w)  (V),    in which R⁵ is a radically polymerizable group, t is an integer from    1 to 5, Sp is a hydrocarbon radical with 1 to 30 carbon atoms, the    carbon chains of the hydrocarbon radical being able to be    interrupted by O- or S-atoms, A is —PO(OH)₂ (phosphonic acid group),    —O—PO—(OH)₂ (dihydrogen phosphate group), —O—PO(OH)R⁶ (monohydrogen    phosphate group) or —SO₃H (sulphonic acid group), R⁶ being a    branched or preferably unbranched C₁-C₂₀; preferably C₁-C₁₂, in    particular C₁-C₆ alkyl radical, a C₃ C₁₀, preferably C₆-C₁₀    cycloalkyl radical or an aromatic C₆ C₂₀, preferably C₆-C₁₀ radical,    R⁶ being able to be substituted or unsubstituted, w being an integer    from 1 to 3;-   and that the polycondensate (1), the monomer (3) or both are    substituted by fluorine.

By halogen is meant, within the framework of this invention, preferably—F, —Cl, —Br and —I. Alkyl groups can be branched or preferablyunbranched. By hydrocarbon radicals which can be interrupted byheteroatoms or functional groups are meant radicals in which theheteroatoms or groups are integrated into the C—C-chains, i.e. arelinked on both sides with carbon atoms. The hydrocarbon radicals can bearomatic, aliphatic or aromatic-aliphatic.

In the case of the components of the above-defined type which containmore than one group with the same name, these groups can be the same ordifferent. For n=3 the silane (I) can carry for example 3 identicalgroups R¹ or three different groups R¹.

The optional substituents of the group R are preferably ester groups, inparticular C₁-C₆ alkyl ester groups, C₁-C₆ alkyl or C₁-C₆ alkoxyradicals, phenyl, —Cl, —Br and —OH, the optional substituents of R⁶ arepreferably C₁-C₆ alkyl, C₁-C₆ alkoxy, halogen, preferably F, Cl or Br,or OH. If R⁶ is an alkyl group, then this is preferably not substitutedby further alkyl groups.

The materials according to the invention are suitable in particular ascoating materials, in particular for natural and artificial teeth,denture parts and orthodontic devices, and are also called dentalmaterials in the following. The dental materials can be applied intra-and extraorally.

Preferred radically polymerizable silanes of formula (I) are defined asfollows:

-   R¹=a vinyl, (meth)acryl, vinylcyclopropyl, allyl or styryl group,-   R²=dispensed with, methylene, ethylene, propylene, butylene,    phenylene, —(CH₂)₂CH—O—OC— (CH₂)₃—CO—NR⁹— (CH₂)₃— or    —[CH₂—CHR⁹—O—OC—(CH₂)₂—]₂N—(CH₂)₃— with R⁹=H or CH₃,-   R³=C₁-C₁₂ alkyl, particularly preferably C₁-C₃ alkyl, in particular    methyl or ethyl;-   X=F, Cl or C₁-C₃ alkoxy, particularly preferably F, methoxy or    ethoxy;-   n=0 or 1-   m=1.

These and the following details are to be taken in each case to meanthat the preferred and particularly preferred definitions of theindividual variables can be chosen independently of each other.Compounds in which all the variables have one of the preferred orparticularly preferred definitions are naturally quite particularlypreferred.

Examples of particularly preferred silanes of Formula (I) are3-(methacryloyloxy)-propyl-triethoxysilane,3-(methacryloyloxy)-propyl-trimethoxysilane,3-(acryloyloxy)propyl-methyl diethoxysilane, vinyl or allyltrimethoxysilane, or reaction products of3-isocyanatopropyltriethoxysilane with 2-hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate or glycerine dimethacrylate.

Further preferred are addition products of 3-aminopropyltriethoxysilaneor 3-mercaptopropyltriethoxysilane to monomers which, along with anacrylate group, contain one or more methacrylate groups, such as e.g.2-methacryloyloxyethyl acrylate or 2-acryloyloxy-1,3-dimethacryloxypropane. Also suitable are amides which are accessible by reaction of3-aminopropyltriethoxysilane with methacrylate carboxylic acids, e.g.reaction products of succinic acid or glutaric acid anhydride with2-hydroxyethyl (meth)acrylate, hydroxypropyl(meth)acrylate or glycerinedi(meth)acrylate.

Preferred silanes of Formula (II) are defined as follow's:

-   R⁴=linear C₁-C₁₂ alkyl, particularly preferably C₁-C₆ alkyl, in    particular methyl, ethyl, propyl, phenyl, the hydrogen atoms of    these radicals being completely or partially replaced by F;-   Y=F, methoxy or ethoxy;-   p=an integer from 1 to 4′, in particular 0.1 to 3.

Particularly preferred examples of silanes of Formula (II) aretetrachloro, tetraethoxy or tetramethoxysilane, CH₃—SiCl₃, CH₃—Si(OC₂H₅)₃, C₂H₅—SiCl₃, C₂H₅—Si (OC₂H₅)₃, phenyl-Si(OC₂H₅)₃,C₃H₇—Si(OCH₃)₃, (CH₃)₂SiCl₂, (phenyl)₂SiCl₂, (CH₃)₂Si(OC₂H₅)₂,(C₂H₅)₃Si—Cl, (C₂H₅)₂Si(OC₂H₅)₂, (CH₃)₃Si—Cl, (CH₃O)₃S₁—C₃H₆—NH₂,(CH₃O)₃Si—C₃H₆—SH, (CH₃O)₃Si—C₃H₆—NH₂. Silanes with p=4 are preferablyused in combination with silanes in which p is 1, 2 or 3.

According to the invention polycondensates (1) are preferred which aresubstituted by fluorine, preferably by 3 to 22 fluorine atoms. These arepreferably obtained by using as component (B) a silane of formula (II),which has fluorine substituents, these fluorine substituents being boundto the radical R⁴. The fluorine atoms are preferably concentrated on assmall as possible a number of neighbouring carbon atoms. Polycondensatesare particularly preferred which contain perfluoroalkyl radicals of theC_(b)F_(2b+1)- or —C_(b)F_(2b)-type, b resulting from the definition ofthe silanes of Formulae (I) and (II).

Preferred fluorine-substituted silanes of Formula (II) are CF₃CH₂CH₂—Si(OC₂H₅)₃, C₂F₅—CH₂CH₂—Si(OC₂H₅)₃, C₄F₉CH₂C₂—Si(OC₂H₅)₃,n-C₆F₁₃CH₂CH₂—Si(OC₂H₅)₃, n-C₈F₁₇—CH₂CH₂—Si(OC₂H₅)₃, CF₃CH₂CH₂—SiCH₃(OC₂H₅)₂ and n-C₆F₁₃CH₂CH₂—O—CO—NH— (CH₂)₃—Si (OC₂H₅)₃.

Preferred metal compounds, of Formulae (III) and (IV), are defined asfollows:

-   Z=C₁-C₄ alkoxy or Cl.

Particularly preferred examples of compounds of Formula (III) areAl(OCH₃)₃, Al(OC₂H₅)₃, Al(OC₃H₇)₃, Al(OC₄H₉)₃ and AlCl₃.

Particularly preferred metal compounds of Formula (IV) are ZrCl₄,Zr(OC₂H₅)₄, Zr(OC₃H₇)₄, Zr(OC₄H₉)₄, ZrOCl₂>TiCl₄, Ti(OC₂H₅)₄, Ti(OC₃H₇)₄and Ti(OC₄H₉)₄.

The compounds of formulae (III) and (IV) can be functionalized bycomplex formation, for example by complexing with acids, preferablypropionic acid, methacrylic acid, maleic acid or succinic acid, orβ-dicarbonyl compounds, preferably acetylacetone, acetoacetic acid or2-acetoacetoxyethyl methacrylate. During the complexing the groups Z arecompletely or partially displaced by the complexing groups of thecomplex formers.

To initiate the radical photopolymerization benzophenone, acylphosphinicoxides, such as 2,4,6-trimethyl-benzoyldiphenyl phosphinic oxide,benzoin as well as their derivates or α-diketones or their derivates,such as 9,10-phenanthrenquinone, 1-phenyl-propane-1,2-dione, diacetyl or4,4-dichlorobenzil are preferably used. According to a particularlypreferred version camphorquinone and 2,2-methoxy-2-phenyl-acetophenoneand α-diketones are used in combination with amines as reduction agent,such as e.g. 4′-(dimethylamino)-benzoic acid ester (EMBO),N,N-dimethylaminoethyl methacrylate, N,N-dimethyl-sym.-xylidine ortriethanolamine.

Azo compounds such as azobis(isobutyronitrile) (AIBN) orazobis-(4-cyan-valerianic acid) or peroxides, such as dibenzoylperoxide, dilauroyl peroxide, tert.-butyl peroctoate, tert.-butylperbenzoate or di-(tert.butyl)-peroxide are particularly suitable asthermal initiators.

Benzopinacol and 2,2′-dialkylbenzopinacols are also suitable asinitiators for hot curing.

Redox initiator combinations, such as e.g. combinations of benzoylperoxide with N,N-dimethylsym.-xylidine or N,N-dimethyl-p-toluidine, areused as initiators for polymerization at room temperature. Moreovercombinations of peroxides with such reduction agents, such as e.g.ascorbic acid, barbiturates or sulphinic acids, are also suitable.

The materials according to the invention can contain, as component (3),organic, radically polymerizable monomers, in particular one or more(meth)acrylates, (meth)acrylamides and/or pyrrolidone derivatives.Suitable for this are, in particular, monomers liquid at roomtemperature (diluting monomers) which have only one polymerizable group,and monomers which have two or more, preferably 2 to 5 polymerizablegroups and effect a cross-linking, of the polymerizate (cross-linkingmonomers). Monomers, with two or more polymerizable groups are alsocalled multifunctional monomers. Component (3) preferably contains atleast one cross-linking monomer. Both diluting monomers andcross-linking monomers can be substituted by one or more, preferably 3to 22 fluorine atoms. The use of fluorinated, i.e. fluorine-substituted,monomers is preferred, and necessary when using non-fluorinatedpolycondensates (1).

The fluorine atoms are also preferably concentrated on as small aspossible a number of neighbouring carbon atoms. Monomers areparticularly preferred which contain perfluoralkyl radicals of theC_(b)F_(2b+1)- or —C_(b)F_(2b)-type, b resulting from the definition ofthe monomers.

Particularly preferred diluting monomers are mono(meth)acrylates, e.g.methyl, ethyl, butyl, benzyl furfuryl or phenyl(meth)acrylate andmesityl methacrylate which is characterized by a high hydrolysisstability, and 2-hydroxyethyl methacrylate (HEMA). Further preferredexamples are N-monosubstituted or N-disubstituted acrylamides, such asN-ethylacrylamide, N,N-dimethacrylamide, N-(2-hydroxyethyl)acrylamide orN-methyl-(2-hydroxyethyl)acrylamide, N-monosubstituted methacrylamides,such as N-ethylmethacrylamide or N-(2-hydroxyethyl)methacrylamide, andN-vinylpyrrolidone, these compounds likewise having a high hydrolysisresistance.

Preferred cross-linking monomers are multifunctional acrylates andmethacrylates, such as bisphenol-A-di(meth)acrylate, bis-GMA (anaddition product of methacrylic acid and bisphenol-A-diglycidyl ether),UDMA (an addition product of 2-hydroxyethyl methacrylate and2,2,4-hexamethylene diisocyanate), di-, tri- or tetraethylene glycoldi(meth)acrylate, decanediol di(meth)acrylate, trimethylolpropanetri(meth)acrylate, pentaerythritol tetra(meth)acrylate, butanedioldi(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12 dodecanedioldi(meth)acrylate, cross-linking pyrrolidones, such as1,6-bis(3-vinyl-2-pyrrolidonyl)-hexane, and bisacrylamides, such asmethylene or ethylene bisacrylamide, bismethacrylamides, such asN,N′-diethyl-1,3-bis(acrylamido)-propane, 1,3-bis(methacrylamido)-propane, 1,4-bis(acrylamido)-butane or1,4-bis(acryloyl)-piperazine, which can be synthesized by reaction ofthe corresponding diamines with (meth)acrylic acid chloride or arecommercially available.

Preferred fluorinated monofunctional monomers are 2,2,2-trifluoroethyl(meth)acrylate, pentafluorethyl methacrylate, 2-(pentafluorbutyl)ethyl(meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate,3-(pentafluorobutyl)-2-hydroxypropyl (meth)acrylate,perfluorocyclohexylmethyl methacrylate,3-(perfluorohexyl)-2-hydroxypropyl (meth)acrylate,2-(perfluoro-3-methylbutyl)ethyl methacrylate,3-(perfluoro-3-methylbutyl)-2-hydroxypropyl(meth)acrylate,1H,1H,5H-octafluoropentyl(meth)acrylate, 1H,1H,2H,2H-pentafluorodecylacrylate, 1H,1H-perfluoro-n-decyl (meth)acrylate,2-(perfluorodecyl)ethyl(meth)acrylate, 2-(perfluoro-9-methyldecyl)ethyl(meth)acrylate, 2-perfluoro-5-methylhexyl)ethyl(meth)acrylate,2-(perfluoro-7-methyloctyl)ethyl(meth)acrylate,1H,1H,7H-dodecafluoroheptyl (meth)acrylate,1H,1H-perfluoroctyl(meth)acrylate,1H,1H,2H,2H-perfluoroctyl(meth)acrylate,1H,1H,9H-hexadecafluorononyl(meth)acrylate and1H,1H,1H-eicosafluoroundecyl(meth)acrylate and 1H,1H,2H,2H-pentafluorodecyl acrylate.

Preferred fluorinated cross-linking monomers are fluorinated triethyleneglycol dimethacrylate (TEGDMA-F), 2,2,3,3-tetrafluoro-1,4-butanedioldimethacrylate, 1H,1H,6H,6H-perfluoro-1,6-hexanediol di(meth)acrylate,1H,1H,10H,10H-perfluorodecanediol di(meth)acrylate,2,2,3,3,4,4,5,5,6,6,7,7,7-dodecafluoro-1,8-octanediol di(meth)acrylateand fluorinated bis-GMA (bis-GMA-F: 2,2-bis[(4-(2-hydroxy3-methacryloyloxy) propyloxy) phenyl]-hexafluoropropane):

By organic, radically polymerizable monomers (3) are meant compoundswhich are not silanes and do not carry any of the acid groups definedfor compounds of Formula (V).

Preferred acid monomers (4) of Formula (V) are defined as follows:R⁵ _(t)-Sp-A_(w)  (V)

-   R=a vinyl, (meth)acryl, (meth)arylamide, styryl group or a group of    Formula (VI)    in which R¹⁰ is H or a branched or preferably unbranched C₁-C₂₀,    preferably C₁-C₁₂, in particular C₁-C₆ alkyl radical, a C₃-C₂₀,    preferably C₃-C₆ cycloalkyl radical, or an aromatic C₆-C₂₀,    preferably C₆ C₁₀ radical, where R¹⁰ can be substituted or    unsubstituted;-   t=1 or 2;-   Sp=C₁-C₁₅ hydrocarbon radical which can be interrupted by O atoms,    preferably 1 to 5 O atoms;-   A=—O—P(O) (OH)₂, —SO₃H, in particular —PO(OH)₂;-   w=1 or 2.

The optional substituents of the radical R¹⁰ are preferably C₁-C₆ alkyl,C₁-C₃ alkoxy, halogen or OH. If R¹⁰ is an alkyl radical, this ispreferably not substituted by further alkyl radicals.

Monomers of Formula (V) are also called acid monomers in the following.

The preferred mono- and dihydrogenphosphoric acid esters capable ofpolymerization include 2-methacryloyloxyethyl-phenyl-hydrogen phosphate,dipentaerythritol-pentamethacryloyloxy phosphate,10-methacryloyloxydecyl-dihydrogen phosphate,dipentaerythritol-pentamethacryloyloxy phosphate and6-(methacrylamido)hexyldihydrogen phosphate.

A preferred phosphonic acid is2-[2-dihydroxyphosphoryl)-ethoxymethyl]-acrylicacid-2,4,6-trimethyl-phenyl-ester.

Preferred sulphonic acids capable of polymerization are vinylsulphonicacid, 4-vinylphenylsulphonic acid and 3-(methacrylamido)propylsulphonicacid.

Quite particularly preferred monomers of Formula (V) are the phosphonicacids vinylphosphonic acid, 4-vinylphenylphosphonic acid,4-vinylbenzylphosphonic acid, 2-methacryloyloxyethyl phosphonic acid,2-methacrylamidoethyl phosphonic acid, 4-methacrylamido-4-methyl-pentylphosphonic acid 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl] acrylic acid.

Polymerizable carboxylic acids, i.e. monomers which contain only acarboxyl group as acid group, are not suitable as acid monomers.According to a preferred version the dental materials according to theinvention contain no polymerizable carboxylic acids, such as(meth)acrylic acid, and preferably also no non-polymerizable carboxylicacids.

The materials according to the invention can, along with the componentsalready named, advantageously contain further components, in particulara filler (5). By adding filler, the mechanical properties of the coatingcan be improved. Fillers with an average particle size of 5 to 60 nm,preferably 10 to 40 nm are preferred. Unless stated otherwise, theparticle size is in each case the particle size established by dynamiclight scattering. Particularly preferred fillers are particulate SiO₂,Al₂O₃, Ta₂O₅, Yb₂O₃, ZrO₂, nanoparticulate silver, TiO₂ and mixed oxidesOf SiO₂, ZrO₂ and/or TiO₂. Particularly suitable are nanoparticulatefillers with an average particle size smaller than 100 nm which aresurface-modified with groups capable of polymerization and, due to theirsmall particle size, do not reduce the transparency of the coating, i.e.do not agglomerate. A surface modification is preferably achieved in thecase of siliceous fillers by silanization, and in the case ofnon-siliceous fillers in the way described in WO 00/69392.

The amount of filler is preferably 0 to 50 wt.-%, particularlypreferably 0 to 20 wt.-% and in particular 0 to 10 wt.-%. All figuresare relative to the total weight of the dental material.

Moreover the materials according to the invention can contain furtheradditives, such as e.g. colouring agents (pigments or dyes),stabilizers, aromatics, microbiocidal active ingredients, solvents,plasticizers or UV absorbers. Preferred solvents are water, ethanol,acetone and ethyl acetate By adding volatile solvents, such as acetoneor ethanol, the wetting behaviour and the film formation can bepositively influenced. These solvents can be used alone or in a mixturewith water.

Cements and filling composites as a rule contain no solvents, adhesivesand coating materials preferably 0 to 20 wt.-%, particularly preferably0 to 10 wt.-% and more particularly preferably 0 to 5 wt.-% solvent, ineach case relative to the total weight of the dental material.

According to the invention materials are particularly preferred whichare comprised wholly of the components defined herein and in particularof the preferred components defined herein.

The polycondensates (1) can be obtained by hydrolytic polycondensationof components A to C in the manner described below, component (A) beingable to be used alone or together with the components (B) and/or (C) forthe preparation of the polycondensates. According to a preferred versionmixtures are used for the preparation of the polycondensates, whichalong with component (A), contain at least one of components (B) or (C),preferrably (B) and (C). Particularly preferred starting mixtures forthe preparation of the polycondensates contain 30 to 70 wt.-% (A) and 5to 70 wt.-% (B), in particular 40 to 65 wt.-% (A) and 15 to 65 wt.-%(B), quite particularly preferably 45 to 60 wt.-% (A) and 20 to 60 wt.-%(B). Component (C) is, if present, preferably used in an amount of 5 to30 wt.-%, particularly preferably 10 to 20 wt.-% (C). The amounts givenrelate to the total weight of the components used for the preparation ofthe polycondensates (1). If only silanes are used as educts, thehydrolytic condensation preferably takes place such that the compoundsto be hydrolyzed are reacted, alone or in presence of solvent andoptionally of a hydrolysis and condensation catalyst, with astoichiometric amount of water or an excess of water. The reaction iscarried out at room temperature accompanied by a gentle cooling or mildheating. The reaction mixture is stirred until the hydrolysis andcondensation have proceeded to the desired degree of conversion, i.e.the monomer starting compounds in the reaction mixture are practicallycompletely consumed, i.e. can no longer be detected by ²⁹Si-NMRspectroscopy. The course of the hydrolytic condensation can be followedusing ²⁹Si-NMR spectroscopy.

If metal compounds (C), in particular compounds of Zr or Al, are usedalong with the silanes, the water is preferably added in portions attemperatures of −30° C. to room temperature. Lower aliphatic alcohols,in particular ethanol, or isopropanol, aliphatic ketones, in particularacetone, esters, in particular ethyl acetate, ether, in particulardiethyl ether or tetrahydrofuran, DMF and amines are particularlysuitable as solvents. Mineral acids, in particular hydrochloric acid orhydrofluoric acid, carboxylic acids, in particular formic acids oracetic acid, sulphonic acids, phosphonic acids and phosphoric acid canbe advantageously used as catalytic acids. The condensation is howeverpreferably initiated by the acid, radically polymerizable monomers (V)alone.

Within the framework of the invention it was surprisingly found that,above all, dihydrogenphosphate esters capable of polymerization and inparticular phosphonic acids not only effect a very fast hydrolyticcondensation e.g. of the silanes, but at the same time promote a wettingof the tooth structure and improve the adhesion to the tooth structure.

According to a preferred version the preparation of the polycondensates(1) takes place by acidolysis of metal alkoxides, e.g. by condensationof trialkoxysilanes, tetraalkoxysilanes, titanates and zirconatesaccompanied by the addition of carboxylic acids, such as e.g. formicacid (cf. e.g. WO 93/2333 or DE 101 06 787 A1). During this reaction thewater required for the hydrolytic condensation forms by reaction of thealkoxides with the acid accompanied by simultaneous formation of metaloxide and ester.

The preparation of the polycondensates can also alternatively take placein the presence of the other components. To this end components (A) andoptionally (B) and/or (C) are mixed with radically polymerizable monomer(4) and optionally (3) solvents and filler and the condensation reactionis then initiated by adding acid and water. An initiator is then addedto the polycondensate-containing mixture for the radical polymerizationand cured by radical polymerization.

Depending on the type and number of hydrolyzable groups of silanes,polycondensates form which show flexible or glass like properties. Thecross-linking density and thus the hardness can be increased for exampleby using tetraalkoxysilanes such as tetraethoxysilane. If the proportionof organic substituents is increased, for example by organicallymodified trialkoxysilanes or dialkoxysilanes, the network becomesincreasingly more flexible, the nature and size of the organic radicalsplaying a role, too. Through the incorporation of Zr, Ti or Al compoundsthe hardness, abrasivity and refractive index of the coating can becontrolled. Through cocondensation of silanes with metal alkoxides,materials with ceramic properties such as e.g. great hardness areobtained. Aluminium oxide leads, to a reduction in abrasivity, theincorporation of the elements titanium and zirconium effects an increasein the refractive index, with the result that this can be set in atargeted way by the amount of corresponding Ti and/or Zr compounds. Therefractive index is moreover dependent on the porosity and crystallinityof the formed polycondensates.

Generally, the polycondensation is preferably controlled so thatpolycondensates liquid at room temperature are obtained as these arepreferred. The homopolymerization of trialkoxysilanes results in mostlyflowable products, solid products can be obtained for example by addingtetraalkoxysilanes.

After the condensation reaction is complete the polycondensates aremixed with the other components of the materials according to theinvention. By polycondensates are meant condensates with more than 2,preferably more than 5 and particularly preferably more than 10 silicon,aluminium, zirconium and/or titanium atoms. The materials preferablycontain no monomeric silanes or disiloxanes.

The materials according to the invention can for example be thermally orphotochemically cured depending on the chosen polymerization initiator.The properties of the cured materials can be varied by differentfactors. The mechanical properties, such as strength and flexibility,can be controlled on the one hand by the network density of the formedcondensates (high proportion of hydrolyzable groups of the compounds (A)to (C) leads to a high network density) and polymerisates (monomers withseveral polymerizable groups lead to a dense three-dimensional network).

The organic spacers can however also make the network more rigid or moreflexible, for example through, development of hydrogen bridge bonds,variation of their length and their functional groups, which can be moreor less flexible. Other properties, such as the refractive index, can bevaried by the spacer groups or e.g. also by the incorporation of metalatoms, such as Zr and Ti. In the case of aliphatic spacer groups, theflexibility of the materials increases as the length of the spacer groupincreases, whereas the incorporation of aromatic spacer groups increasesthe rigidity of the cured materials. The water adsorptivity of thematerials can be increased or reduced by spacers with hydrophilic orhydrophobic groups.

The properties of the coating can be further influenced by varying thecross-linking density, i.e. by changing the number of groups capable ofpolymerization of the silanes or of the optionally further added organicmonomers.

The materials according to the invention contain at least onepolycondensate or a radically polymerizable monomer which is substitutedby fluorine. According to a preferred version the materials contain botha polycondensate and a radically polymerizable monomer which issubstituted by fluorine. By using fluorine-containing components, inparticular fluorosilanes and fluorinated monomers, a reduction of thesurface energy of the materials and thus a reduction of the accumulationof plaque can be realized. Since, as a rule, these components accumulateat the boundary layer, only a comparatively small proportion of thesecomponents is necessary to achieve the desired effect. Materials whichcontain 5 to 10 wt.-% fluorine relative to the total weight of the curedcomposition are preferred.

On the other hand the fluorine-containing components endow the materialswith hydrophobic properties, which clearly makes a wetting of the toothsurface difficult and adversely effects the adhesion of the materials tothe tooth surface. The materials according to the invention, do not havethese disadvantages. By mixing the above named components materials weresuccessfully prepared which on the one hand effectively prevent theaccumulation for example of plaque, but on the other hand show a goodwetting capability for hydrophilic surfaces and good adhesionproperties, i.e. two opposite properties combine with each other. Thisis a surprising improvement vis-à-vis known materials.

The materials according to the invention are applied to the surface tobe coated for example by spraying-on, immersion or painting, e.g. with abrush. Application can take place one or more times. When theapplication is repeated it is advantageous to dry the previously appliedlayer first, for example by evaporating off any solvent present and/orby radical polymerization, and only then apply the next layer. Afterapplication the materials are cured by radical polymerization.

The materials are suitable in particular for the coating of artificialand in particular natural teeth and denture parts. As a rule artificialteeth contain composite materials with a (meth)acrylate polymer matrixand filler, mostly based on SiO₂. Moreover the materials are alsosuitable for the coating of dental plastics, such as prosthesis plasticsbased on polymethyl methacrylate (PMMA), PMMA- or composite-basedmaterials for temporary crowns and bridges, composite filling materials,composite facing and skeleton materials, orthodontic plates andactivators (based on PMMA), dental metal alloys and ceramics. As long asnatural, teeth are not involved, the substrates are preferably in theform of dental prostheses, such as complete or, partial prostheses,artificial teeth or orthodontic devices. Methods of coating suchsubstrates are likewise a subject of the invention. These comprise thesteps:

-   (i) preferably cleaning of the surface to be treated, for example by    degreasing or polishing;-   (ii) application of a material according to the invention;-   (iii) curing of the applied material by radical polymerization;-   (iv) preferably removal of the inhibition layer.

The process according to the invention is characterized in that, apartfrom the optional cleaning, no pre-treatment of the surface with aprimer is necessary. It is particularly advantageous that, when treatingnatural teeth, no conditioning of the tooth surface by acid treatmentand consequently no protection of tooth surfaces not to be treated withprotective coatings is necessary.

By an inhibition layer is meant a thin later of uncured material whichforms because atmospheric oxygen diffuses into the surface of thematerial, as a rule to a depth of roughly 100 μm, and inhibits thepolymerization there. This inhibition layer is preferably removed with asuitable solvent, such as an alcohol, preferably an aqueous alcoholicsolution, particularly preferably an ethanolic solution. The informationof an inhibition layer can be prevented by suitable measures whichprevent the access of oxygen to the treated surface for example bylaying an oxygen-impermeable film or by working in an oxygen-freeatmosphere.

The treatment of natural teeth preferably takes place in the waydescribed in the following. The treatment can serve for therapeuticpurposes, for example for the prophylactic treatment of caries orperiodontitis, gingivitis, hypersensitivities, or for purely cosmeticpurposes, e.g. for preventing tooth discolorations or for brighteningdiscoloured teeth. Furthermore the treatment can serve to protect teethduring dental treatments or provide mechanical protection against ageingprocesses, such as abrasion and cracking. For treatments which arecarried out intraorally, photochemically curable materials arepreferred.

Before the application of the dental materials according to theinvention, above all on areas of the tooth surface threatened by caries,such as the approximal surfaces, areas near the gingiva and exposednecks of teeth, the tooth surface is thoroughly cleaned, e.g. with arubber cup and a cleaning paste, such as are used for professional toothcleaning. Existing dental calculus is removed if necessary. Thenresidues of the cleaning paste are removed, the tooth surfaces to betreated are thoroughly rinsed with water and then dried with an air jet.A contamination of the surface by saliva is preferably prevented byintroducing cotton rollers. Then the dental material is applied to thesurfaces in the form of a thin layer, e.g. with a so-called microbrush,a soft brush or other suitable aids. After an action time of 10-20seconds each coated tooth surface is irradiated for 20-40 seconds(depending on the lamp output) with a polymerization lamp common in thedental field. Then optionally further layers of the material are appliedand then, after the cotton rollers are removed, rinsed once again withwater.

A further subject-matter of the invention are kits which contain all thematerials necessary for the application of the materials according tothe invention. Kits are preferred which, along with the polymerizablematerial, contain an application aid, e.g. a pencil or a brush. Theactual material(s) is (are) housed in suitable, i.e. preferably air- andlight-tight, containers.

The invention is explained in more detail in the following usingembodiments.

EXAMPLE 1 Preparation of Dental Materials Based on Fluorinated Silanesand Acid Monomers

For the preparation of the materials shown in Table 1, three solutionswere prepared in each case and these were then mixed together.

Solution 1 consisted of the amounts of MEMO, PFOTEOS listed in each caseand 40% of the stated amount of HEMA or MMA. In the case of samples 2and 4 monodisperse SiO₂ (13 nm primary particle size), dispersed inTEGDMA, was also added as filler.

Solution 2 consisted of the amounts of BisGMA listed in each ase and 40%of the stated amount of HEMA or MMA.

Solution 3 consisted of the amounts of MA-154 listed in each ase and 20%of the amount of HEMA or MMA.

Solution 1 was mixed with solution 2, then added to solution 3 and thewhole mixture was stirred for 5 mins at room temperature and for afurther 2 mins at 50° C. A condensation of the silanes MEMO and PFOTEOStakes place. The condensation was carried out without water being addedand relatively highly fluid varnishes were obtained. 0.5° wt. %4-dimethylamino)-benzoic acid ester, 0.4 wt. % camphorqiuinone and 0.2wt. % 2,4,6-trimethyl-benzoyldiphenyl phosphinic oxide (Lucerin TPO)were additionally added to the samples, so that the materials were ableto be cured with blue light. TABLE 1 Dental materials based on monomericsilanes and acid monomers Composition (Figures in wt. - %) No. BisGMAMMA HEMA TEGDMA MEMO PFOTEOS MA154 Filler Initiator 1 21.27 21.27 — —20.88 21.24 14.24 — 1.1 2 15.96 16.18 — 15.37 15.81 16.08 11.21 8.29 1.13 22.64 — 20.79 — 20.70 20.96 13.81 — 1.1 4 16.47 — 16.85 12.48 15.9116.12 12.75 8.32 1.1BisGMA: 2,2-Bis-[4-(2-hydroxy-3-methacryloxy-propoxy)phenyl)propaneMMA: methyl methacrylateHEMA: 2-hydroxyethyl-methacrylateTEGDMA: triethylene glycol dimethacrylateMEMO: methacryloxypropyl trimethoxysilanePFOTEOS: tridecafluoroctyl triethoxysilaneMA154: 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid

EXAMPLE 2 Preparation of a Dental Material Based on Fluorinated Silane(Comparison Example)

A dental material of the following composition was prepared Thiscontained tridecafluoroctyl triethoxysilane (PFOTEOS) as fluorinatedsilane, but no acid monomer within the meaning of the invention. Inspite of this, an acid monomer not according to the invention(methacrylic acid) was used. The preparation of the material took placeanalogously to DE 41 18 184 A1 (Example 1). TABLE 2 Dental materialsbased on monomeric silane (Comparison material) Component Proportion[mol] MEMO 0.9 PFOTEOS 0.1¹ Methanol 3.0 Water 1.6 Zr(OPr)₄ ² 0.1³Methacrylic acid 0.2¹corresponds to 10 wt. - % fluorine-containing silane²70% in PrOH³relative to Zr

EXAMPLE 3 Determination of the Abrasion Behaviour

Cleaned, extracted bovine incisors were used for the examination of theabrasion behaviour. The tooth surface was rinsed with water and dried inan air flow. Varnishes No. 1 to No. 4 were applied to the teeth andcured by being irradiated for 20 seconds with a polymerization lamp(Astralis-7). The thus-prepared incisors were then exposed to a fourhour-circular toothbrush movement (bearing force 1N) in a toothbrushsimulator (TBS). A dentifrice paste was used which in its scouringeffect corresponded to a toothpaste cream customary in the trade (RDA75). The wear after the simulated toothbrush treatment was ascertainedanalogously to the method described in DIN ISO 11609. This treatmentcorresponds to a tooth cleaning over a period of roughly 2 years, if itis assumed that each tooth is cleaned twice a day for 10 seconds each.In the all the examined samples the varnish layer applied to the toothwas largely worn away after 4 hours. In none of the examined samples wasthere however an extensive detachment of the varnish from the toothsurface. The tooth varnish adhered to the tooth surface during the totalabrasion test.

EXAMPLE 4 Determination of the Adhesion to Bovine Tooth Enamel

For examining the adhesion of the materials to dentine, bovine teethwere treated with material No. 1 and the results compared with theenamel adhesion of commercially available, light-curing,single-component tooth varnishes based on multifunctional acrylates andmethacrylates (Luxatemp® Glaze & Bond, DMG, Hamburg; Heliobond®, IvoclarVivadent AG, Liechtenstein). A polysiloxane was also prepared accordingto DE 41 33 494 and tested. The bovine teeth were embedded in plasticcylinders so that the dentine and the plastic were located on one plane.Then the tooth surfaces were thoroughly rinsed with water. Then a layerof material No. 1 or of the tooth varnishes customary in the trade wereapplied to the teeth with a microbrush, the varnish layer dried briefly,with an air jet and irradiated for 40 s with a halogen lamp (Astralis 7,Vivadent). The tooth surfaces were not conditioned with acid. Acomposite cylinder of Tetric® Ceram (Ivoclar Vivadent) was polymerizedonto the varnish layer in two layers each of 1-2 mm. The thus-treatedteeth were stored in water for 24 h at 37° C. and the shear adhesivestrength was then determined according to ISO/TS11405. The measurementvalues found are shown in Table 3. TABLE 3 Adhesion to bovine toothenamel (without acid treatment) Material Adhesion value [MPa]¹ MaterialNo. 1 5.8 ± 1.0 Luxatemp ® Glaze & Bond² 0.9 ± 0.9 Heliobond ®² 1.0 ±1.0 Example 2² 2.1 ± 0.5¹Adhesive strength according to ISO/TS 11405²ComparisonThe adhesion values of the material according to the invention lieclearly above those of the comparison materials. The results show that,with the materials according to the invention, without additional acidtreatment of the tooth surface, adhesion values can be achieved whichcorrespond to those for glass ionomer cements which are used for examplefor fixing crowns.

EXAMPLE 5 Determination of the Contact Angle

To ascertain the anti-adhesion properties of the materials according tothe invention the contact angle of distilled water on the film surfacewas measured with a contact angle measuring device (Model DAT 1100,Fibro System AB, Sweden). To this end cylindrical samples with adiameter of 20 mm and a thickness of 2 mm were prepared and exposed tolight for 2×3 min (Spectramat, Ivoclar Vivadent). The non-polymerizedlayer on the surfaces of the samples was removed with ethanol and then 5measurements were carried out on each sample. The average values of themeasurements are given in Table 4 below. Dental coating materialscustomary in the trade based on a methacrylate mixture (Luxatemp® Glaze& Bond, DMG, Hamburg; Heliobond®, Ivoclar Vivadent) and a materialaccording to Example 2 served as a comparison.

As is clear from Table 4, samples 1 to 4 show contact angles which liewell above those of the comparison materials customary in the trade. Itfollows from this that the surface energy and thus the danger of plaqueformation for the samples 1 to 4 according to the invention is clearlyless than for these comparison materials. Although the materialaccording to Example 2 likewise produces a high contact angle, it has,as was shown above, a clearly-poorer adhesion. TABLE 4 Contact anglesfor materials according to the invention determined with distilled waterMaterial Contact angle No. 1 94 No. 2 90 No. 3 94 No. 4 90 Luxatemp ®Glaze & Bond¹ 70 Heliobond ®¹ 69 Example 2¹ 93¹Comparison

1. Polymerizable material which contains (1) 1 to 80 wt.-% of at leastone polycondensate based on (A) one or more radically polymerizablesilanes of Formula (I)(R¹ _(a)—R²)_(m)R³ _(n)SiX_((4-m-n))  (I),  in which R¹ is a radicallypolymerizable group, R² is absent or is a di- or trivalent, substitutedor unsubstituted hydrocarbon radical with 1 to 30 carbon atoms, thecarbon chains of the hydrocarbon radical being able to be interrupted byone or more heteroatoms, one or more carboxylic acid ester groups(—CO—O— or —O—CO—), carboxylic acid amide groups (—CO—NR⁷— or —NR⁷—CO—with R⁷=H or C₁-C₅ alkyl), urethane groups (—HN—CO—O— or —O—CO—NH—)and/or amino groups (—NR⁸— with R⁸=H or C₁-C₅ alkyl), R³ is a C₁-C₁₂alkyl or C₃-C₁₂ cycloalkyl radical, C₆-C₁₂ aryl radical, C₆-C₁₂arylalkyl, C₆-C₁₂ alkylaryl, X is halogen or a C₁-C₃ alkoxy radical, ais 1 or 2, m is an integer from 1 to 3 and n is an integer from 0 to 2,where the sum of m and n can not be greater than 3, and optionally (B)one or more silanes according to Formula (II)R⁴ _((4-p))SiY_(p)  (II),  in which R⁴ is a C₁-C₁₂ alkyl radical orphenyl radical, which can be substituted by —F in each case, Y ishalogen or a C₁-C₃ alkoxy radical, and p is an integer from 1 to 4,and/or (C) one or more metal compounds of Formulae (III) and/or (IV)AlZ₃  (III)Me(O)_(r)Z_(s)  (IV),  in which Z is halogen or a C₁-C₆ alkoxy radical,Me is zirconium or titanium, r is 0 or 1, s is an integer from 1 to 4,the sum of the valencies of the radicals O and Z corresponding to thevalency of the metal, (2) 0.1 to 5 wt.-% of one or more initiators forthe radical polymerization and (3) 0 to 60 wt.-% further radicallypolymerizable monomer characterized in that the material contains inaddition (4) 1 to 50 wt.-% of one or more radically polymerizablemonomers of Formula (V),R⁵ _(t)-Sp-A_(w)  (V), in which R⁵ is a radically polymerizable group, tis an integer from 1 to 5, Sp is a hydrocarbon radical with 1 to 30carbon atoms, the carbon chains of the hydrocarbon radical being able tobe interrupted by O or S atoms, A is —PO(OH)₂, —O—PO(OH)₂, —O—PO(OH)R⁶or —SO₃H, R⁶ being a branched or unbranched C₁-C₂₀ alkyl radical, aC₃-C₁₀ cycloalkyl radical or an aromatic C₆-C₂₀ radical, R⁶ being ableto be substituted or unsubstituted, w being an integer from 1 to 3; andthe polycondensate (1), the monomer (3) or both are substituted byfluorine.
 2. Polymerizable material according to claim 1, characterizedin that the polycondensate is based on at least one silane of Formula(I), in which at least one variable has one of the following meanings:R¹=vinyl, (meth)acryl, vinylcyclopropyl, allyl or styryl, R²=is absent,methylene, ethylene, propylene, butylene, phenylene,—(CH₂)₂CH—O—OC—(CH₂)₃—CO—NR⁹—(CH₂)₃— or—[CH₂—CHR⁹—O—OC—(CH₂)₂—]₂N—(CH₂)₃— with R⁹=H or CH₃, R³=C₁-C₁₂ alkyl,X=F, Cl or C₁-C₃ alkoxy, n=0 or 1, m=1.
 3. Polymerizable materialaccording to claim 1, characterized in that the polycondensate is basedon at least one silane of Formula (II), in which at least one variablehas one of the following meanings: R⁴=linear C₁-C₁₂ alkyl, the hydrogenatoms of R⁴ being completely or partially replaced by F; Y=F, methoxy orethoxy; p an integer from 1 to
 4. 4. Polymerizable material according toclaim 1, characterized in that the polycondensate is based on at leastone metal compound of Formulae (III) and/or (IV), in which Z is C₁-C₄alkoxy or Cl.
 5. Polymerizable material according to claim 1,characterized in that it contains at least one radically polymerizablemonomer of Formula (V), in which at least one of the variables has oneof the following meanings: R⁵=is a vinyl, (meth)acryl, (meth)arylamide,styryl group or a group of Formula (VI)

in which R¹⁰ is H or a branched or unbranched C₁-C₂₀ alkyl radical, aC₃-C₂₀ cycloalkyl, or an aromatic C₆-C₂₀ radical, R¹⁰ being able to besubstituted or unsubstituted; t=1 or 2; Sp=C₁-C₁₅ hydrocarbon radicalwhich can be interrupted by O-atoms; A=—O—P(O)(OH)₂, —SO₃H, —PO(OH)₂;w=1 or
 2. 6. Polymerizable material according to claim 1, characterizedin that it additionally contains (5) 0 to 50 wt.-% filler with anaverage particle size of 5 to 60 nm.
 7. Polymerizable material accordingto claim 1, characterized in that the silane of Formula (II) issubstituted by fluorine.
 8. Polymerizable material according to claim 1,characterized in that it contains at least one further radicallypolymerizable monomer (3) which is liquid at room temperature and has aradically polymerizable group.
 9. Polymerizable material according toclaim 1, characterized in that it contains at least one furtherradically polymerizable monomer (3) which has two or more radicallypolymerizable groups.
 10. Polymerizable material according to claim 1,characterized in that it contains at least one further radical monomer(3) which is substituted by fluorine.
 11. Method comprising applying amaterial according to claim 1 as a coating of teeth, dental prosthesesor orthodontic devices.
 12. Method according to claim 11, wherein thecoating is applied in a manner sufficient for the preventative treatmentof caries, periodontitis, gingivitis and/or hypersensitivities of teeth.13. Method according to claim 11, wherein the coating is applied in amanner sufficient for cosmetic purposes.
 14. (canceled)
 15. Method forthe coating of a substrate surface in which (i) the surface to betreated is cleaned, (ii) a material according to claim 1 is applied; and(iii) the applied material is then cured by radical polymerization. 16.Method according to claim 15, characterized in that an inhibition layeris removed following step (iii).
 17. Method according to claim 15,characterized in that it does not include an acid treatment of thesubstrate surface.
 18. Method according to claim 15, for the therapeuticor cosmetic treatment of natural or artificial teeth, wherein thesubstitute is a natural or artificial tooth.
 19. Kit containing amaterial according to claim 1, the material being housed in an air- andlight-tight container.
 20. Kit according to claim 19, further containingan application aid for the material.
 21. Polymerizable materialaccording to claim 2, wherein R³=methyl or ethyl; or X=F, methoxy orethoxy.
 22. Polymerizable material according to claim 3, whereinR⁴=methyl, ethyl, propyl, or phenyl.
 23. Polymerizable materialaccording to claim 5, wherein R¹⁰ is a C₁-C₆ alkyl radical; C₃-C₆cycloalkyl, or an aromatic C₆-C₁₀ radical; or Sp=C₁-C₁₅ hydrocarbonradical which can be interrupted by 1 to 5 O-atoms.